Quimica Spramolecular Chapter 8 M.J. Lehn Supramolecular Chemistry

8.
2 Supramulecular Photochemistry 93
ET
ME
Fig . 18 . Light-conversion photochemical
molecular device, consisting of two compo-
nents, a light collector (or antenna, light-
absorbing groups A) and a light emitter E . and
performing a three-step process : absorption
(A), energy transfer (ET), and emission (E) .
mized for a given purpose (wavelength of absorbed or emitted light ; lifetime of

emission, etc .) . This is the case for a light-conversion molecular device consisting of
two discrete components, a light collector (or antenna), formed by an array of
strongly absorbing units and an emitter, thus allowing the separate optimization of
absorption and emission . In order to function, intercomponent energy transfer must
occur (as efficiently as possible) . Thus, such a device operates in a three-step mode :
absorption-energy transfer-emission (A-ET-E, Fig . 18) .
This has been realized in luminescent cryptates of europium(m) and terbium(111)
with macrobicyclic ligands [2 .74, 2 .75), such as that in structure 20, which incorpo-
rate various heterobiaryl groups (2,2'-bipyridine, phenanthroline [2 .71, 2 .73,
8 .4-8.7], bithiazole, biimidazole, bipyrimidine [8 .8], biisoquinoline [8 .5, 8 .6], and
their NN'-dioxides; [8 .9-8 .11]) serving as light-collecting antenna components .
These complexes present a unique combination of features arising from both their
cryptate structure and the nature of the emitting species : protection of the included
ion from deactivation due to interaction with solvent (water) molecules ; very high
thermodynamic stability and kinetic inertness ; multiple photosensitizing groups
suitable for ET and displaying strong UV light absorption ; characteristic long wave-
length and long lifetime of the emission . They display a bright luminescence in
aqueous solution whereas the free ions do not emit under the same conditions .
Absorption of UV light by the organic antenna groups is followed by energy trans-
fer to the included lanthanoid cation which then emits its characteristic visible radia-
tion [2.74, 2 .75, 8 .2, 8 .8-8 .15] . The corresponding A-ET-E process is shown for the
Eu(m)-cryptate in 87.
Higher conversion efficiency and stronger luminescence arc found for europium
cryptates such as 88 containing N-oxide ligands [8 .10, 8.11] . In the solid state, com-
plex 87 exhibits especially efficient energy-conversion (about 60%) [8 .16] . This is
also the case for the corresponding Tb(m) cryptate up to about 100 K ; at higher tem-
perature, energy migration and back-transfer from the ion to the cryptand decreases
the emission intensity (8 .17) . Since the nature of the ligand groups strongly influ-
ences the photophysical properties, it may be possible to tune them to the desired
purposes by suitable structural variations . Related macrocyclic complexes display
94 8 Molecular and Supramolecular Devices
h v' Eu3 + included
87 88
89a 89b
analogous luminescent proerties [8 .18]. Di- and trinuclear complexes, such as

those derived from the sodium cryptates 89a [8 .19a] and 89b [8.19b], would offer
further developments for energy transfer studies .
Photoactive cryptates are of interest as novel luminescent materials (in solution
or in the solid state) and as labels for biological applications subject to very strin-
gent constraints (labelling of monclonal antibodies, of oligonucleotides, of mem-
brane components, cytofluorimetry, etc .) [8 .20] . Linked, cascade systems perform-
ing very long range energy transfer (VLRET) may be imagined .
Of particular interest is the development of homogeneous immunoassays based
on cryptate 87 as label . They make use of a second, long range energy transfer

8 .2 Supramolecxlar Photochemistry 95
between a group 87 and an acceptor A (such as allophycocyanine) borne each by a

specific antibody to different epitopes of the antigen as represented in 90 (antibod-
ies bearing 87 and A: left and right ; antigen : centre) [8 .21a, b] ; this process also
results in signal amplification . Such immunoassays present great value for medical
diagnostics [8 .21c] . Europium or terbium complexes of crown ethers [8 .22] and of
a calixarene [8 .23] display similar ET luminescence processes . Photochemical com-
munication by ET or eT may take place between a luminescent metal complex borne
by a /3-cyclodextrin core and a guest molecule included in the receptor cavity [8 .24] .
ET
<01-L 90
Polymetallic complexes presenting directional energy migration are of much sig-

nificance for the design of photochemical molecular devices . Large arrays of multiple
photoactive and redox-active building blocks (of ruthenium- or osmium tris(bipyri-
dine)-type for instance) have been constructed for such purposes [A . 10, 8 .25-8 .27] .
Intramolecular transfer of excitation energy occurs in molecules containing
several chromophores such as pyrene, anthracene or porphyrin groups connected
by various linkers [8 .28, 8 .29] . Energy and photoinduced electron transfer proces-
ses (see Section 8 .2 .3) are found in bichromophoric supermolecules assembled
through hydrogen bonding recognition via base pairing [8 .30, 8 .31] .
Ultrafast energy hopping takes place in multichromophoric /3-cyclodextrin de-
rivatives [8 .32] and triplet energy migration occurs in solid and liquid-crystalline
phases of substituted phthalocyanines [8 .33] . In the former case, very efficient ET
from the multiple collector antenna leads to strong luminescence of an acceptor dye
included in the cavity [8 .32c] . Such results are of much interest for the design of
inorganic or organic photochemical devices presenting directional energy migra-
tion, as was shown to take place in a photonic molecular wire built on a rigid linear
array of porphyrin units [8 .32d] .
8.2 .2 Photosensitive Molecular Receptors
Receptor molecules bearing photosensitive groups may display marked modifica-

tions in their photophysical properties on the binding of substrate species, leading
to changes in their light absorption (e .g ., colour generation) or emission features and
allowing their detection by spectroscopic measurements [8 .34-8 .41] (see also Sec-

I

S
tion 6 .4 .3) . They represent molecular devices for substrate-selective optical signal
generation and for optical reading-out of recognition processes . Such photo-che-
mosensors make possible the development of sensitive analytical methods for the
detection of specific substrates [8 .42] .
Chromo- or lumino-ionophores of macrocyclic or macropolycyclic type res-
pond to the binding of metal ions [8 .34-8 .41] and may be of much interest as ana-
lytical tools, for instance, for environmental applications or for the study of ionic
changes in biological processes such as cell signalling [8 .41] . Receptors such as 91-93
combine the strong and selective complexing ability of cryptands with the intense
absorption or emission properties of photosensitive groups like azophenol
[8 .43-8 .45], spirobenzopyran [6 .65], anthracene [8 .37, 8 .46, 8.47] or coumarin [8 .48,
8 .49] . They display marked changes in absorption and fluorescence on complex-
ation of alkali-metal cations or protonation, thus acting as fluorescent signalling
systems (that may involve photoinduced electron transfer quenching [8 .39, 8 .40,
8 .46]), for instance in a very selective colourimetric assay of lithium in serum [8 .43b]
(see also [8 .50, 8 .51]) . Photoresponsive substances derived from other types of
receptors like spherands [8 .52] and calixarenes [8 .53], present related properties . I
X
N
eN (L0 \_
/ )) I
0
0 0l I
~ ~0 O~J
r-\
I
`N N
0 OJ
\_j
91 92

ᖻ.2 Supramolecular Photochemistry ᖻᖻ
The macrotricyclic receptor ᖻ2 displays fluorescence detection of linear recognition

of diammonium cations due to changes in monomer-excimer emission [ᖻ .ᖻᖻa] and
the bis-naphthyl macrotricycle in ᖻ2 gives an extremely strong fluorescence en-
hancement on protonation, being thus a very sensitive proton sensor [ᖻ .ᖻᖻb] . Simi-
lar optical detection processes operate in the recognition of barbiturate by a lumi-
nescent bis-pyrene ligand [ᖻ .ᖻᖻa] and in the selective colouration of a spiropyran
derivative on binding of guanosine derivatives [ᖻ .ᖻᖻb] . Fluorescent sensors may also
be derived from cyclodextrins [ᖻ .ᖻᖻ] .
Photosensitive receptors for anionic substrates have been reported [ᖻ .2ᖻ, ᖻ .ᖻᖻ] .
Of special interest is the strong enhancement of the acridine fluorescence observed
when ATP binds to a receptor molecule formed by a [2ᖻ]-N ᖻ02 macrocycle bearing
a lateral acridine group, as shown in ᖻ2 [ᖻ .2ᖻ] ; guanosine triphosphate slightly
decreases the emission . Thus, this receptor is a sensitive and selective ATP probe
that generates a fluorescence signal on ATP binding . Such features may be of use for
monitoring ATP levels and reactions involving ATP [ᖻ .ᖻᖻ].
Photoresponsive receptor molecules present features that allow the development
of molecular recognition dependent optrodes [ᖻ .ᖻ2, ᖻ .ᖻᖻ, ᖻ .ᖻ0], optical sensors for
the continuous monitoring of specific substrates in organisms, in the environment,
etc .
Finally, one may note that the variations in the beautiful colours of flowers due
to anthocyanins result from supramolecular effects, namely copigmentation, intra-
molecular sandwich-type stacking and intermolecular association [ᖻ .ᖻ1] .
ᖻ.2.ᖻ Photoinduced Electron Transfer in Photoactive Devices
Light absorption, by markedly affecting the electronic properties of molecules and

metal complexes, may induce intra- or intermolecular electron transfer processes
leading to electron-hole separation .
The photogeneration of charge-separated states by photoinduced electron trans-
fer (PeT) is of interest for initiating photocatalytic reactions (e .g ., natural and arti-
ficial photosynthesis) and for the transfer of photosignals (e .g ., through a mem-
brane) . It may be realized in a three component entity containing a photosensitizer
PS linked to an electron donor D and an electron acceptor A, possessing suitable
redox properties in their ground and excited (for PS) states so that irradiation of PS
leads to electron transfer from D to A yielding the charge separated triad D+-PS-A-
(Figure 1ᖻ) .
Numerous systems of this type, such as the carotenoid-porphyrin-quinone triad
ᖻᖻ [ᖻ .ᖻ2a] (for PeT in a pentad see [ᖻ .ᖻ2b]), have been extensively studied in many
laboratories from the photochemical point of view and as models of natural photo-
synthetic centres [ᖻ .ᖻ2-ᖻ .ᖻᖻ, A . 10, A .20], especially in order to achieve very fast
charge separation [ᖻ .ᖻᖻ] and slow recombination, for instance in multiporphyrin

EXCITATION I by
y JMNl
D art; PS : ~,;:-~ A
ELECTRON TRANSFER RECOMBI NATION

I
;f! • ;
i
CHARGE SEPARATED STA-=
Fig. 19 . Schematic representation of a center for photoinduced charge separation consisting

of a photosensitizer PS, a donor D and an acceptor A as well as insulating spacer groups [8 .2] .
0
® H) _
/ i S\
(CHZ)
(Cµr)m C-H 11 tip
•,
®
94 a
complexes [8 .69c] . In this respect, organized supramolecular assemblies have been

used to separate the D, PS and A components and influence the rates of forward and
reverse electron transfer processes so as to yield long lived charge-separated states
[8 .68] .
The D, A or PS units may be metal coordination centres . Metal to ligand charge
transfer (MLCT) in metal complexes (such as Ru(II) or Re(i)-diimine centres) has
been extensively used for generating PeT processes [8 .64-8 .68, A .10, A .20] . Our
own work has been concerned with photoinduced charge separation in macropoly-
cyclic coreceptors containing both a photosensitive porphyrin group and binding
sites for silver(i) ions as acceptor centres . Thus, complexation of silver ions by the

8.2 Suprarnolecular Photocbemistry 99
lateral macrocycles, as shown in 95, results in quenching of the singlet excited state
of the Zn-porphyrin centre by an efficient intracornplcx electron transfer, from the
porphyrin to Ag(i), leading to charge separation and generating a porphyrinium
cation of long lifetime [8 .70a] .
(
0 O
0 .
O
o
, O
95
Long range thermal and PeT processes are of particular interest in both chemistry
and biology (see also Section 8 .3 .2) . Rigidly linked components allow the investi-
gation of the geometrical factors influencing electron transfer [8 .71a,b, A .10, A .20] .
Electron hopping occurs in polynuclear assemblies of metal complexes bound, for
instance, to a polymer support [8 .71c] . Specific PeT effects take place in restricted
reaction spaces, between groups on the surfaces of micelles, in dendrimers or bound
to the DNA double helix [7,83] .
Systems undergoing photoinduced electron-transfer processes represent compo-
nents for light-to-electron conversion devices . Of special interest is the design of
systems performing long-range electron transfer (see Section 8 .3 .2), in order, for
instance, to generate transmembrane photoelectric signals or to serve as the basis of
an electronic shift register memory at the molecular level [8 .72] .
8 .2.4 Photoinduced Reactions in Supramolecular Species
Receptor molecules containing suitable light-sensitive groups may undergo photo-

induced structural and conformational changes that affect their binding properties
[6 .63-6 .65] . As a consequence, substrate uptake or release occurs, representing a
way to generate protonic or ionic (or molecular) photosignals in light-to-ion con-
version devices .
Receptor-substrate binding may affect the photochemical reactivity of either or
of both species . The recognition process could thus modify the course of a reaction,

affecting its rate or the nature of the products, and give rise to novel transforma-
tions.
The complexation of coordination compounds may make it possible to control
their photochemical behaviour via the structure of the supramolecular species form-
ed . For instance, the binding of cobalt(m) hexacyanide by macrocyclic polyam-
monium receptors markedly affects their. photoaquation -quantum yield in a struc-
ture-dependent manner [8 .73-8 .77] . It thus appears possible to orient the photo-
substitution reactions of transition-metal complexes by using appropriate receptor
molecules . Such effects may be general, applying to complex cations as well as to
complex anions [2 .114] .
The course of a number of other photoreactions could be altered or oriented by
selective binding . In particular, substances effecting single- or double-strand nucleic
acid recognition and fitted with a photoreactive group may perform sequence spe-
cific photocleavage [4 .56, 5 .29, 5 .30] .
The incorporation of photoactive compounds into organized supramolecular
assemblies allows the induction of specific reactions and structural changes such as,
for instance, in the photocrosslinking of photopolymerizable components in lipid
vesicles, a powerful approach to the control of polymolecular architectures [7 .10,
8 .78] .
8.2 .5 Non-Linear Optical Properties of Supramolecular Species
Organic and inorganic substances presenting a large electronic polarizability are

likely to display marked optical non-linearities that depend first on molecular fea-
tures [8 .79-8 .84], but novel effects should arise on going to the supramolecular level
[8 .85, 8 .86] .
Non-linear optical (NLO) properties are considered to result from both the in-
trinsic characteristics of the molecules and from their arrangement in a material
(solid, powder, monolayer or multilayer film) . An intermediate stage should also be
taken into account, that of the supermolecules, where the association of two or more
components may yield more or less pronounced NLO effects . Thus, three levels of
non-linear optical properties may be distinguished corresponding to the molecule,
the supermolecule and the material . The molecular level involves intramolecular
effects and structures, whereas at the supramolecular level intermolecular interac-
tions and architectures come into play together with collective effects in the mate-
rial [8 .85, 8 .86] . Incorporation into supramolecular arrangements may perturb the
electronic properties of individual molecules and impose a specific orientation,
namely by recognition induced self-organization .
The design of molecules, supermolecules and materials presenting NLO activity
involves molecular and supramolecular engineering . At the molecular level, a high
polarizability, leading to large quadratic f3 and cubic y hyperpolarizability coeffi-

8.2 Suprarnolecular Photochemistry 101
cients, is sought . At the supramolecular level, it is necessary to achieve a high

degree of organization, such as found in molecular layers, films, liquid crystals,
the solid state, which may be generated by molecular recognition and inclusion
complex formation . Both features are required for materials to display pronounc-
ed second order NLO effects ; the structure must also be non-centrosymmetric,
due either to the molecular components themselves or to their arrangement in the
condensed phase . On the other hand, centrosymmetric species present third order
but no second order NLO properties . In addition, bulk characteristics such as
stability, preparation, processing and mechanical features will determine the prac-
tical usefulness of a given material (for general presentations see for instance
[8 .79-8 .84]) .
Of special interest arc push-pull polyenes composed of a polyolefinic chain bear-
ing a donor group on one end and an acceptor on the other (see 96) . Push-pull caro-
tenoid derivatives (Figure 20) are highly polarizable conjugated polyenes that also
represent polarized molecular wires .
They display intramolecular charge transfer [8 .87] and marked second-harmonic
generation . The determination of the hyperpolarizabilities of such compounds
96
C
Me2 N
® -k q
V
acceptor groups A
CN
N CN
A ® 0 NO2
CN
Fig . 20 . Two series of donor-acceptor polyconjugated molecules bearing a ben7 .odirhia or

a dimcthylaminophcnyl group as donor D and a variety of acceptor groups A .

yields exceptionally large values for the longer ones [8 .88, 8 .89] and provides insight
into the dependence of quadratic and cubic hyperpolarizabilitics on chain length
and on substituents [8 .83, 8 .90, 8.91] .
The incorporation of such compounds into mixed Langmuir-Blodgett films built
from a fatty acid (see 97) [8 .92] or from an amphiphilic cyclodextrin [8 .93] produces
oriented arrangements presenting marked NLO features .
97
If a highly polarizable group is introduced into a receptor molecule, substrate

binding should cause substantial perturbations, so that the recognition event would
be converted into a non-linear optical signal . Such recognition-dependent non-
linear optical probes may be derived for instance from polycnes such as those shown
in Figure 20, from inclusion complexes [8 .94a] or from donor-acceptor calixarenes
[8 .94b] .
Other polyunsaturated substances such as oligothiophenes [8 .95a] or dyes
[8 .95b] as well as organometallic or coordination compounds [8.85, 8.95c] may also
present pronounced NLO properties .
The D-PS-A systems investigated for their ability to yield charge-separated sta-
tes possess suitable features (see Section 8.2 .3) . Ion-dependent optical changes pro-
duced by indicator ligands [8 .34-8 .40] could lead to ion-selective control of non-
linear optical properties . Molecular electron donor-acceptor complexes may pre-
sent NLO effects since they possess polarized ground states and undergo inter-

8.2 Supramolecular Photochemistry 103
molecular charge transfer on excitation . It is possible to more or less finely tune their
polarization, polarizability, extent of charge transfer, absorption bands, etc ., by
many variations in basic structural types as well as in substituents .
It is clear that combining the design of NLO active molecules with the manipu-
lation of selective intermolecular interactions may produce novel NLO materials
that take into account supramolecular features .
8.2 .6 Supramolecular Effects in Photochemical Hole Burning
Dye molecules incorporated in a crystalline or amorphous (polymer or glass) solid

matrix are located in different environments and therefore present a distribution of
absorption frequencies whose envelope results in a broad absorption band . When
such dye doped media are irradiated with laser light under conditions where the
guest species are frozen in their environment (very low temperature), given mole-
cules are selectively affected so that very narrow and stable "holes" can be "burned"
into the absorption band . Such photochemical hole burning in condensed materials
is, because of its very high resolution, of great interest for high density optical stor-
age [8 .96-8 .100] .
The effects between dopant and matrix are clearly of supramolecular nature and
each dye molecule with its surrounding matrix species may be considered to repre-
sent a supermolecule [8 .98, 8 .100]. Thus, hole burning is specifically a supramolec-
ular photochemical process . As a consequence, the manipulation of intermolecular
interactions [8 .101] and recognition processes in the condensed phase could allow
the designed generation of a range of environmental distributions, as well as induce
specific changes in the absorption features of the dye molecules . Thus, taking into
account explicitly the supramolecular effects opens ways to control the environ-
mental features in hole burning experiments .
A number of far-reaching applications have been envisaged from ultra-narrow
optical filters to high density optical storage (beyond 10 8 bits/cm 2) [ 8 .96, 8 .99], to
holography and to optical "molecular computing" [8 .98, 8 .100, 8 .102] . Optical data
processing with bacteriorhodopsin displays very interesting features [8 .99, 8 .103] .
Room temperature and single molecule hole burning represent exciting recent
developments [8 .99] .
The photochemical and photophysical processes discussed above provide illu-

strations and incentives for further studies of photoeffects brought about by the f or-
mation of supramolecular species . Such investigations may lead to the development
of photoactive molecular and supramolecular devices, based on photoinduced
energy migration, electron transfer, substrate release, or chemical transformation .
Coupling to recognition processes may allow the transduction of molecular infor-

104 8MolecuarndSpmolecuarDvis
mation into photosignals .Thusmolecardign,stvermolcuabndig,

andsuprmolec ahiturswpohyical,toem andpicl
proetisabughoetr,ildngupecot-dn supramolec
photonics.
8 .3 MolecuarndSpmolecuarEtniDevcs
Muchateniosbgvtheposiblyfdvepngchmialsyte
capbleofhndigctrsawyeminctoflrimpnets .Ven-
extnsivworkhabepfmdonlctraive lsuchaorgnimetls
(e .g ., condutigplymersandchgtfersal)[8 .104-8 .106)ormlecua
semicondutr[8 .107]thamyledovicsbanrg mteials [8 .108] .
Insuchblkompndsuralc eftsouringbewthspc
formingthealpyofcurseanimpt ole .
Ontheorad,psibltyhaenvisgdto elcrnidvs
thawouldperthvofemlcuandthspermolcu .Thisdefn
afield of molecuar and supramolec elctronis conerigthp sof
singlemocu,figmolecuarsitondfplymecuarhits
suchaLngmir-Blodetfs [7 .2, 7 .3, 7 .78, 7 .79, 8 .109-8 .112, A .43] withnad
betwnhiclrotansfepc[8 .113] may occur.Torealizsuch
devicsnol rateps .Itisfrnecaytoimg cpnetmolu
thamypose dirfatus,ynheiz adstuy proei .The
secondtpi roateinsuprmoleca hiturs,came-
branesothgizedsruct,anoivesgtwhr esulingt-
typose hrquidpoets .Thetirdspqu hecontif
basicuntohermpnts,iorde a tvirelymocuswithan
extrnalphysic g .Pursingthed ofmlcuaretni curyma
havemnyspi-ofalgthewy,inadotrsingvelqutosab he
handligofmecus .Itisprobalyemtu rodfineclaythrous
tohegal ;inde,thf o egalitsfmychngeudrtiflc
of progesmadlnivepth(foraiw of thercnaivsthefld
se[8 .114, 8 .115]).
Theposibltyfdgnevicsuhamolrectifs[8 .116], tran-
sitor,wcheandpotis benvagdsomftherquida-
turesapnicomudshaetlcompxsrD-PSAytemsha
leadtophinucargesption hlevftisoadmlecu ([8 .62] ;
seSction 8 .2 .3) .Theadvntofsiglcrnthaoceprsinvolg
asinglectro ganicmrostue[8 .17a]ledstohcnira of
molecuarntics[S .117b] .

8.3 Molecular and Supramolecular Electronic Devices 105
8.3 .1 Supramolecular Electrochemistry
Molecular devices operating on electrons are basic elements for converting molec-
ular recognition events into electronic signals . Redox properties may be affected by
binding in a structure-dependent manner. Such perturbations by complexation lead
to an electrochemical characterization of recognition . Electrochemical effects re-
sulting from receptor-substrate binding define a domain of supramolecular electro-
chemistry .
Redox responsive receptor molecules arc based on two types of component : sub-
strate binding sites and electroactive groups . A number of substances have been
studied in which the redox properties of groups such as metallocenes [6.50b,
8 .118-8 .121], quinones [6 .50a, 8 .122] or paraquat [8 .123] are modified on substrate
binding (see also Section 6.4 .1). Conversely, redox interconversion of these groups
allows the reversible switching between states of high and low affinity . The mutual
effects of redox changes and binding strength in a receptor-substrate pair thus may
make it possible to achieve electrocontrol of complexation and, conversely, to
modify redox properties by binding .
The electrochemical properties of redox-active substrates are also affected on
binding to a receptor molecule . This is the case for the complexation of metal
hcxacyanides by polyammonium macrocycles where the shift of the redox poten-
tial depends on the binding constants and the oxidation or reduction of the sub-
strates leads to pronounced changes in stability (see Chapter 3) [3 .21, 3 .22] .
As a consequence of these electrochemical effects, molecular receptors may be
used to convert the chemical information present in binding and recognition pro-
cesses into electronic signals [8 .124-8.127]. They allow the development of substrate
specific sensors, based on chemically sensitive thick or bilayer membranes [6 .6,
8.125], and semiconductor devices [8 .126, 8 .127] such as field effect transistors
(PET) . Conversely, one may envisage performing electrochemically controlled, se-
lective release of a given substrate from a material, for instance for drug delivery
[8 .128] . Ultramicroelectrodes [8 .129] represent means for addressing small scale
electrochemical changes .
Multinudear metal complexes possess a rich electrochemistry [8 .130a] and may
serve as electron reservoirs. Organic redox systems containing multiple electro-
phores effect electron storage and transfer [8 .130c] . Thus, dinuclear Cu(1) [4.7] and
Ni(n) [8 .131] complexes exchange two electrons in one step and four electrons in
two steps, respectively. Attachment of several redox groups such as ferrocene [8 .132,
8 .133], viologen [8 .134] or Ni(it) cyclam [8 .135] to a core provides electron reser-
voirs that may be capable of powering multielectron catalytic reactions . Polyoxy-
metallates also take up a number of electrons (up to 32) [8 .136] . Biological multi-
redox centres are found, for instance, in the electron transfer protein cytochrome c~
that contains four heme groups [8 .137], whose redox properties are affected by local
solvatron as in synthetic porphyries [8 .138] .

Systems presenting many identical redox-active components bound to a central

core or assembled by specific interactions represent approaches towards molecular
batteries, i .e ., molecular devices capable of performing the reversible exchange (stor-
age and release) of many electrons at the same potential .
8 .3 .2 Electron Conducting Devices . Molecular Wires
Among the various devices and components performing molecular-scale electronic

functions that may be imagined, a crucial one is a molecular wire, which might oper-
ate as a connector permitting electron flow to occur between the different elements
of a molecular electronic system .
Three main classes of electron transfer processes may be considered : (1) electron
transport by redox active molecules acting as mobile carriers through membranes ;
this may or may not also involve electron transfer from one carrier to another during
an encounter ; (2) electron hopping between suitable redox active groups attached to
a backbone or assembled via non-covalent interactions ; (3) electron conduction
along a continuous conjugation path formed by zt-bonds, which may also involve
other electron transmitting groups such as strained o-bonds, etc . ; it represents an
electron channel, and embodies specifically the idea of a molecular wire .
The components effecting these processes may be either organic or inorganic .
The two extreme cases (1) carrier mediated and (3) channel-mediated electron trans-
fer are represented in Figure 21 . The first is coupled to the flow or the counterflow
of a positively or a negatively charged species, respectively ; it has been considered
in Section 6 .4 . Numerous studies on electron transfer across vesicle bilayer mem-
branes have been performed, employing a variety of effectors, especially in view of
the relations to biological electron transfer [6 .44-6 .46, 8 .139] .
The design of a molecular wire should satisfy three criteria : (1) contain an elec-
tron-conducting chain ; (2) possess terminal clectroactive and polar groups for re-
versible electron exchange; (3) be long enough to span a typical molecular support-
ing element such as a monolayer or a bilayer membrane (Figure 21, right) .
M'
e-
Fig. 21 . Transmembrane electron transfer processes : carrier mediated via a redox carrier
(left) or channel mediated via a molecular wire (right) . Both processes may be coupled to light
by introduction of photoactive groups in the carrier or in the wire .

8.3 molecular and Supramolecular Electronic Devices 107
Our first approach towards the design of molecular wires was based on the caro-
viologens (CV 2 +), long, conjugated polyolefinic chains bearing pyridinium groups
at each end, which combine the structural features of carotenoids with the redox
properties of methylviologen . Such compounds (e .g.; 98) were synthesized and
shown to be incorporated in a transmembrane fashion into bilayer vesicles [8 .140],
as is also the case for other carotenoids bearing terminal hydrophylic groups [8 .141] .
The orientation of caroviologens in model lipid membranes was studied by linear
dichroism measurements . Dichroic ratios were determined on caroviologens of dif-
ferent lengths solubilized in lyotropic lamellar phases of different thicknesses and
macroscopically aligned between quartz plates . The orientation parameters obtain-
ed indicated transmembrane arrangement for caroviologens of length compatible
with the bilayer thickness of the membrane [8 .142] .
98
Electron-transfer experiments employing the CV2+/dihexadecyl phosphate

vesicle system did not give positive results, perhaps because of the high negative
charge of the membrane surface, which may modify the redox potential of incor-
porated CV22+ and reduce interfacial electron transfer rates . However, on incorpor-
ation of zwitterionic caroviologens CV2± such as compound 99 into phospholipid
vesicles, electron transfer occurred between an external reducing phase and an inter-
nal oxidizing phase (Figure 22) . Using only a small amount of incorporated 99
(about 150 active molecules per vesicle) an acceleration factors of 4-8 over back-
ground was obtained . This clearly indicated that CV 2± 99 did induce electron con-
duction [8 .143] . Pulse radiolysis studies provided information about the reduced
CV*' [8 .144a] and neutral CV species (see also [8 .144b]) that are expected to be
intermediates in the process.
5038
99

Fig. 22 . Schematic representation of transmembrane electron transfer from a reducing

agent (such as sodium dithionite) to an oxidizing agent (such as potassium ferricyanide) by a
zwitterionic caroviologen such as 99 incorporated in the Waver membrane of a phospholipid
vesicle [8 .143] .
But But Bu' Bu' Bu' Bu' Bu' But
B"I * / \ 0 Bow * 11 0 Bu'Bu' l 10 Bu'But * l, 4 Bu'
I H \ ~N 1 H \ ~N ~N I H ~ N N H N
I N N I N N` ` ` 1 ~N N` N
N 1 0 N N N N-
H r N_ N N
Bu' Bu'Bu' 0 - Bu t Bu' ® - 0 But Bu' Bu'
if * * P 0
Bu' But out Bu' Bu' Out But But
100
Thus, the caroviologen approach does produce functional molecular wires that
effect electron conduction in a supramolecular-scale system . Incorporation into
black lipid bilayer membranes (BLM) should allow further investigations of the
electron-transfer properties of these caroviologens and positive preliminary results
have been obtained [8 .145a] . A theoretical investigation of electron conduction in
molecular wires has been made [8 .145b] .
Other promising approaches to molecular wires involve linear conjugated arrays
of porphyrins (e .g ., 100) [8 .146], a bis-flavin amphiphile [8 .147], oligothiophenes
[8 .148, 8 .149] and long, rigid aromatic molecules (e .g., 101) [8 .150] that form persis-
tent reduced species [8 .151a] and oriented Langmuir-Blodgett films [8 .151b] .
Tetrathiafulvalenes, basic components of "organic metals", have been used as build-
ing-blocks of supramolecular entities [8 .152] . One may note that species based on

• 0 M 0 M 0 0 k N 0
.3F
®
• +.+.+•r 00
N ® N
0
*0*00
A, 0 u 0
®
00
N ®.,®i N 4
Ceieh
u 0 Ar 0
101
J 11 _ .
102
103
bicyclo[1 .1 .1]propellane ("staffanes") [8 .153], bicyclo[2 .2 .2]octane [8 .154] and car-

borane [8 .155] components offer linear rigid frameworks for the oriented arrange-
ment of redox active groups .
Since caroviologens are rather fragile compounds, they can be protected from the
environment by inclusion into polyanionic derivatives of (3-cyclodextrin in a
rotaxane fashion 102 [8 .156] . Also, in the design of molecular devices, it may be
desirable to introduce some extent of redundancy in order to reduce the risk of
device failure . This is the case in the tris-carotenoid macrobicycle 103 that represents
a sort of triple-threated molecular "cable" whose crystal structure 104 has been
determined . It forms a dinuclear Cu(i) complex 105 in which the bound ions intro-
duce a positive charge at each of the species, a feature of potential interest for trans-
membrane inclusion [8 .157] .
The development of electronic circuity will require the relative positioning of
components . This has been investigated, for instance, through orthogonal connec-
tion of two oligothiophenes via spiro junctions (e .g ., 106) [8 .158, 8 .159] . Electron

104
105
n-B n-B n-Bu -Bu
M93Sl SIMe3
S S S S S
Me3Si / \ \ / 1 / `3
n-B n-Bu n-B u n-Bu
106
relaying between groups in substances containing many redox centres [8 .160] may
be used for electrically "wiring" enzyme redox centres to electrodes [8 .161] . Min-
iaturization [8 .129] and surface functionalization of electrodes [8 .162] with suit-
ably selected molecular units provide ways towards the electrical addressing of
devices.
Electron transfer processes play a major role in biology and their mechanisms
have been very actively investigated in order to gain information about the struc-
tural factors affecting transfer rates and directionality [8 .163] . A series of appro-
priately derivatized cytochrome c protein molecules revealed that electron transfer
rates correlate with the length of tunnelling pathways comprising covalent bonds
and hydrogen bonds as well as through-space jumps [8 .164] . The DNA double helix
may serve as support for photoactive electron donor and acceptor groups [7 .83b] .
Such results also provide information of great value for the design of artificial elec-

tronic wires for oriented electron transfer over long distances in molecular and
supramolecular systems . It depends on a number of features for which optimization
conditions have been analysed to achieve ultrafast and highly efficient processes
[8 .165, 8 .166] .
8.3 .3 Polarized Molecular Wires . Rectifying Devices
Conjugated polyolefinic chains bearing an electron-acceptor group on one end and

a donor on the other end (e .g ., 96) represent polarized molecular wires that should
display preferential one-way electron transfer and could act as a rectifying compo-
nent . Such molecules, donor-acceptor carotenoids (Figure 20), were prepared and
shown to possess very pronounced non-linear optical properties in powder form,
in solution, or in Langmuir-Blodgett films (see Section 8.2 .5) . Oriented incorpora-
tion into organized assemblies [8 .92, 8 .93] and electron-transfer experiments might
reveal one-way conduction by polarized molecules of this or similar type .
Approaches to organic rectifiers have been made using D-6-A species containing
a donor and an acceptor group linked by an insulating covalent tf bridge [8 .116] . A
system based on a conjugated D-n-A unit incorporated in molecular layers has been
reported [8 .116c] as well as a bilayer rectifier at clay-modified electrodes [8 .116d] .
Theoretical analyses of electron transfer through such a single chain molecular wire
have been given [8 .116e] . Species of this type may contribute to the development of
a molecular transistor .
8.3 .4 Modified and Switchable Molecular Wires
Future developments in the design of molecular wires may concern three main fea-
tures : (1) modifying the conduction component, replacing the polyolefinic structure
by units such as connected or condensed oligothiophenes, oligopyrroles, aromatic
groups or metal coordination centres, for instance (see Section 8 .3 .2); (2) varying the
redox active end groups, which may also serve to anchor the device to a surface or into
a membrane ; (3) arranging the wire units into organized arrays orcircuits through link-
ing to a structural framework or by self-assembly based on recognition processes
[8 .167] .
Attaching metal centres (such as ferrocene groups, pyridine or 2,2'-bipyridine
complexes) at the end of a polyconjugated chain would provide molecular wires
combining the rich electrochemical and photochemical activities of metal complexes
with the long-range conjugation properties of the chain, thus leading towards
systems capable of performing electro- or photoinduced long range electron trans-
fer (LReT). Coupling molecular wires with photoactive groups is expected to yield
photoresponsive electron channels . Species of the D-PS-A type (see Section 8 .2 .3)

may act as photoactivated molecular wires in bilayers [8 .168] capable of generating

LReT, charge separation and signal transfer .
Carotenoid chains bearing metal complexes as terminal groups, metallocaroten-
ates, such as 107 and 108, belong to this class [8 .169] . Thus despite a large metal-
metal separation, 108 presents electronic coupling between the terminal subunits
both in the Ru(ii) Runt) mixed valence complex and in the triplet state of the bis-
Ru(n) complex [8 .170] . Bis-Ru(111) (NH3)5 complexes of bis-pyridine polyenes also
display features resulting from the properties of the metal centres [8 .171] . The
bridging ligand controls the extent of electronic communication between terminal
metals [8 .172] . A ferrocene unit introduced into donor-acceptor type conjugated
systems, as in 109, may serve as donor centre or redox switch in films deposited on
electrodes [8 .173] . Substances of such types, which incorporate electro- and photo-
Fe
Fe
.WW
107
Rti (bpy)2
108
H37C\8
N
I
H37C18
Fe
CN
s2L7~\
NC
109

8.4 Molecular and Supramolecular Ionic Devices 113
sensitive switches at the end of or inside the conjugated chain, represent switchable
molecular wires (see Section 8 .5 .2) responding to external stimuli .
8.3 .5 Molecular Magnetic Devices
Molecular magnetism [8 .174] is by essence of supramolecular nature since it results

from the collective features of components bearing free spins and on their arrange-
ment in organized assemblies or solid lattices . The engineering of molecular mag-
netic systems requires the search for high-spin components of organic (such as free
radicals, carbenes or charge-transfer salts), organometailic [8 .174-8 .177] or inorgan-
ic (metal coordination centres [8 .178, 8 .179]) nature and their arrangement in suit-
able supramolecular architectures so as to induce spin coupling and alignment . Of
special interest is the search for molecular ferromagnetism towards which signifi-
cant progress has been made [8 .174-8 .176, 8 .179] .
It is clear that the design of molecular free-spin components and the supramolec-
ular control of spin coupling in three dimensions represents a major area of investi-
gation towards magnetic devices and novel magnetic materials that may be of great
interest for information storage and processing .
8.4 Molecular and Supramolecular Ionic Devices
The numerous receptor, reagent, and carrier molecules capable of handling inor-
ganic and organic ions are potential components of molecular and supramolecular
ionic devices that would function via highly selective recognition, reaction, and
transport processes with coupling to external factors and regulation . Such compo-
nents and the devices that they may build up form the basis of a field of molecular
Tonics, the field of systems operating with positively or negatively charged ionic spe-
cies as support for signal and information storage, processing, and transfer. In view
of the size and mass of ions, ionic devices may be expected to perform more slowly
than electronic devices. However, ions have a very high information content by
virtue of their multiple molecular (charge, size, shape, structure) and supramolec-
ular (binding geometry, strength and selectivity) features .
Molecular ionics offers a promising field of research that may already draw from
a vast amount of knowledge and data on ion binding and transport by natural and
synthetic receptors and carriers . The molecular recognition events involved may be
directly related to information and signal processing by ions, as is the case in biol-
ogy [8 .180, 8 .181] . Indeed, biological signals and communication events are based
on ionic and molecular species (sodium, potassium, calcium, chloride, acetylcholine
ole ul r nd upr mole ul r evi es
ions et hile the interest of omponents oper ting with photons nd ele trons
is well re ognized one m y m ke spe i l se for the development of mole ul r
toni s s ounterp rt to mole ul r photoni s nd ele troni s nd wide open
pl yground for the design of ion or mole ule sed devi es
ele tive ion re eptors represent si units for ioni tr nsmitters or dete tors
sele tive ion rriers orrespond to ioni tr nsdu ers hese units m y e fitted with
triggers nd swit hes sensitive to extern l physi l light ele tri ity he t pressure
or hemi l other inding spe ies regul ting sites stimuli for onne tion nd
tiv tion
inding tr nsport nd triggering m y e performed y sep r te spe ies e h
h ving spe ifi fun tion s in multiple rrier tr nsport systems see e tion
his llows v riety of om in tions etween photo or ele tro tive omponents
nd different re eptors or rriers ight nd redox sensitive groups in orpor ted
into re eptors nd rriers ffe t inding nd tr nsport properties
ore eptors nd o rriers provide me ns for regul tion vi of tors
o ound spe ies th t modul te the inter tion with the su str te hus simple
ioniz le group su h s r oxyli id fun tion represents proton swit h nd
le ds to proton g ted re eptors nd rriers responding to p h nges s seen for
inst n e in the regul tion of tr nsport sele tivity y see lso e tion
n lyti l methods sed on opti l or ele tri l effe ts indu ed y ion inding nd
tr nsport h ve een developed see e tions nd
on tr nsfer t kes pl e through mo ile rriers or ion h nnels see h p
ter ig rot ting shuttle pro ess m y lso e onsidered rtifi i l tr ns
mem r ne h nnels h ve een mu h less explored th n rriers pro ly e use
of the inherently l rger mole ul r stru tures involved despite the f t th t iol
ogi l tr nsport is thought to o ur m inly vi h nnel type spe ies
rious routes to the design of ion h nnels nd ion responsive mem r ne systems
h ve een investig ted some of them h ve lre dy een mentioned ove e tion
ne m y im gine v riety of ion h nnel types depending on the n ture of
the ion inding sites on the w y in whi h they re rr nged on the mole ul r
type nd on the over ll stru tur l fe tures ome re represented s hem ti lly in
igure
ppro hes to rtifi i l ion h nnels h ve for inst n e m de use of m ro y li
units see lso elow of peptide nd y li peptide
omponents of non peptidi polymers nd of v rious mphiphili mole
ules he properties of su h mole ules in orpor ted in il yer
mem r nes m y e studied y te hniques su h s ion ondu t n e p t h
l mp or me surements owever the n ture of the
superstru ture formed nd the me h nism of ion p ss ge rrier h nnel pore
defe t r diffi ult to determine nd often rem in m tter of onje ture
n ddition to ttempts t onstru ting ion h nnels on the sis of multi on
ne ted polyether m ro y les we h ve investig ted m inly two ppro hes

TYPES of ION CHANNEL STRUCTURES
STACK STRING RACK PIPE SPRING SPLIT BUNDLE BOUQUET
Fig. 23 . Schematic representation of different possible types of ion channel structures (from
left to right) : stack, string, rack, pipe of macrocycles, helical strand, two half-channel units,
self-aggregated and macrocycle core bearing bundles of chains .
towards the design of molecular structures that may function as ion channels and
lead to ion-responsive membrane systems : tubular mesophases and "bouquet mo-
lecules" . Self-assembling structures will be considered below (Section 9 .4) .
8 .4 .1 Tubular Mesophases
A stack of macrocyclic rings defines a molecular tube through which ions might
flow, as illustrated by a solid-state model of such an ion channel [6 .71] . Since in dis-
cotic liquid crystals, the spontaneous axial stacking of molecular discs gives colum-
nar mesophases, it appeared that if such phases could be obtained with ring elements
displaying an internal void, their arrangement in an axial stack would yield a hollow
column, that is, a molecular tube 110 . Macrocyclic polyamines bearing suitable side
chains, such as 111 and 112, indeed give tubular mesophascs that contain stacks of
macrocycles [8 .194, 8 .195] . Photocyclization of cinnamoyl derivatives of 111 yields
covalently linked columnar aggregates [8 .195] . Although the macrocyclic elements
used at present are not well suited for ion binding, further elaboration could lead to
ion channels that would be phase (temperature) dependent and could therefore also
present non-linear ion transfer behaviour .
Channel-like architectures are formed in the mesophase given by complexes of
long chain crown ether derivatives [8 .196a,b] and long-chain calixarene derivatives
display columnar liquid-crystalline arrangements [8 .196c] . Self-assembled tubular
structures based on cyclic peptide components have been described [8 .186] .

~N 7
N N
~` R _N ~~R
tip„ R" N `' N ~R
N CR
(N N)
% OF R/N
R [ L R
LN N-)
f>~f~
R V__/(\~ \ R
R
R=p-n-C 12 H 25 0-C 5 H 4 -CO
110 111 112
Ionic conductivity has been established with flexible polymers of polyethylene

oxide) type [8 .197]. The more rigid components of tubular mesophases or solid state
macrocyclic structures may allow fast ion propagation if a smooth profile of the
interaction potential for ion migration along the stack of macrocycles can be estab-
lished . This may require incorporating the counteranion into the framework and
employing ion binding sites that form loose rather than strong complexes . The lat-
ter would be expected to cause local trapping of the ions in a potential well . Molec-
ular modelling should provide helpful information about the design of such struc-
tures . Similar considerations apply to the potential ion channels that could be form-
ed by the stacking of polyether macrocycles borne by phthalocyanine [8 .198-8 .201],
porphyrin [4 .68], peptide [8 .202] or polymeric [6 .72] backbones . Cooperative ion
binding has been found to occur in such multisite species [8 .201] .
8 .4.2 Ion-Responsive Monolayers
Deposition of macrocycles bearing lipophilic side chains at the air-water interface

could yield ion-responsive molecular films .
Indeed, macrocyeles 111 and 112 form such monolayers [8 .195, 8 .203] . Compar-
ison of measured surface areas with molecular models indicated that the macro-
cycles were lying flat on the water surface while the aliphatic chains were tilted
upright in the compressed film, as shown in Figure 24 [8 .203] . Monolayers contain-
ing binding units may interact selectively with ions or other substances present in
the subphase [8 .204] .
Various developments may be envisaged, in particular towards monolayers
effecting ion recognition at an interface (of interest, for instance, for selective detec-
tion and sensors, see Section 8 .4 .5) or ion-binding, electro- or photoactive films .

cc~ o
~N /-\ N--)
r N-CC
`N NJ
OC ~~ NCO
oc co
N--,
~
CN N-C
O p
-\,N N**
~6..J
Oc `Co a
Fig . 24 . Schematic representation of the arrangement of macrocvcle III in a compressed film at the air-waterinterf ace ; the aliphatic chains
are represented in thcir fully extended form, but some curling may occur .
8.4 .3 "Bouquet"-Type Molecules and the "Chundle" Approach

to Molecular Channels
A channel may be delineated by a bundle of transmembrane chains, formed either

by the spontaneous association of individual molecules (e.g ., the polymolecular
channel formed by the peptide alamethicin [6 .67, 6 .68]) or by grafting several chains
onto a supporting unit such as a polyfunctional macrocycle that constitutes the
organizing core, as represented by the "bouquet"-shaped entity 113 . This has been
termed the chundle approach to a transmembrane channel based on a bundle of
chains . Suitable "bouquet" entities should present three main features : (1) two
bundles of chains long enough to span half a membrane bilayer, (2) a central annu-
lus serving both as support to maintain the two bundles of chains and as substrate-
selection component, and (3) terminal polar groups for anchoring the molecule to
each interface in a transmembrane fashion .
O O
O O
db O O
113
"Bouquet"-shaped molecules based on either a polyether +nacrocycle [8 .205] or

a f3-cyclodextrin ((3-CD) [8 .206] core, such as 114 and 115 respectively, have been
synthesized and their polycarboxylate forms have been incorporated into vesicle
bilayer membranes [8 .207] . They present structural features suitable for studies of
chundle-type molecular channels : (1) the functionalized cyclic annulus possesses
substrate selection properties ; (2) it bears axially oriented bundles of oxygen-con-
taining chains, which provide binding sites for metal cations and are long enough
for the molecule to span a typical lipid membrane (the overall length with the chains

RO ' _
O Oy OR RO O
0~ OR
(~ 0
O
0_ 'o of
~o
0 NHJt, HN O
O~ .NN f NNvO TN/ 'N~
N N O
0'# 1 0 0
0 NH
H N„ 0 0
0
O ,
HN~"O V^'O-^/ O :L NH
0 ® 10 0 0 0
MeO 0
0"N-~ HN"0 ~N~O
OI 10
OI ZO
~6
O~OR RO~001OR
AO" '0
in an extended state may be estimated to lie in the 45-50 A range) ; (3) the terminal
carboxylate groups allow for anchorage at water-membrane interfaces and trans-
membrane orientation, as well as for eventual coupling to proton gradients .
When incorporated into the phospholipid membrane of liposomes, compounds
114 and 115 increased the permeability to Na -- and Lit ions, and ion transfer pro-
ceeded by a cation-cation antiport mechanism (Figure 25) [8 .208] .
Variations in the bouquet molecule including changing from poly(oxyethylene)
to polymethylene chains and changing from a crown ether annulus to a cyclodex-
trin (CD) annulus did not have strong effects on ion-transport activities . A carrier
mechanism could be excluded for the compounds studied since ion-transport
activity was undiminished in membranes in the gel state [8.208] . However, the
results gave no firm indication about the exact mechanism of the process, whether
it involved passage through the interior of the molecules or occurred through a pore
induced by aggregation of several molecules, as is the case for the pore-forming
polyene antibiotics (e .g., amphotericin, candicidin, nystatin, etc .) [8 .209] . Models of
the latter have been investigated as channel forming structures [8 .210] .
Fig. 25 . Schematic representation of the transport experi-

ment in which aqueous NaCI solution is added to a prepa-
ration of liposomes containing bouquet molecules in the
membrane in aqueous LiCl solution, creating opposing gra-
dients in Na+ and Li+ ion concentrations . The entry of Na'
ions, initially found only in the external volume, into lipo-
somes is followed by 23 Na NMR spectroscopy ; the exit of
Li4 may also be followed by 7 Li NMR spectroscopy.
The "bouquet"-type compounds 114 and 115 and related molecules thus form
functional ion transfer entities . Further studies are required to ascertain the mecha-
nism of transport and the effects of parameters such as membrane composition,
nature of alkali metal ions and concentration of bouquet molecules on the transport
rate in order to better describe the mode of action of these compounds . Ion trans-
port by "bouquet"-type molecules related to 114 and bearing lateral macrocyclic
units has been investigated [8 .188] .
A very large molecule such as 115 bearing seven chains on each side of the rigid
/3-CD core of about 6 A diameter and 400 A3 internal volume is of interest in itself
[8 .206] . By its size, its internal space, and its chains, it represents a sort of molecular
vesicle formed not by self-assembled amphiphilic chains but by chains covalently
grafted on a central core . Because it is dissymmetric, this /3-CD chundle could act
as an oriented transmembrane device . Its transfer selectivities might have analogies
with those of the channel of the acetylcholine receptor . Physical, chemical, mem-
brane-incorporation, and substrate-transfer properties of this and other /3-CD deri-
vatives will provide basic information about the handling and the behaviour of large
functional molecular species . Whatever the efficiency of the present or other
chundle molecules as ion channels, they nevertheless allow the testing of approaches
to channel design and to the handling of selective ionic conduction .
Incorporation of molecular ionic devices into supporting structures (such as
membranes, layers, and films) allows the exploration of their functional properties
and of their ability to produce ionic signals . Regulation of flow, switching, and
coupling to other components will require further structural modifications . Co-
operative effects and regulation of ion binding may be produced with ligands con-
taining two or more sites for the same or different substrates [8 .182, 8 .211, 8 .212],
whereas photoresponsive ligands provide switching capacity (see Section 8.5) .

8 .4 Molecular and Supramolecular Ionic Devices 121
8.4 .4 Molecular Protonics
The proton, being the smallest ion and the elementary particle counterpart of the
electron, deserves special attention . The designed handling of protons defines afield
of molecular protonics, whose development and features may parallel those of mo-
lecular electronics, Despite the much higher mass of the proton compared with that
of the electron, the rates of proton transfer can be very fast especially if tunnelling
processes are involved . On the other hand, the extremely wide range of proton
transfer rates may be considered an asset for the design of protonic devices . Molec-
ular protonics thus represents a particularly interesting special case of molecular
ionics . Proton transfer and gradients are of basic importance in bioenergetics, where
they drive transport processes and ATP synthesis, and in the chemiosmotic scheme
[8 .213] .
Numerous processes may be linked to proton transfer and protonation/depro-
tonation reactions (for general descriptions of proton transfer see, for instance,
[8 .214-8 .217]) . Proton-triggered yes/no or +/- switching is contained in the ability
of polyamine receptors and carriers to bind and transport cations when unproton-
ated and anions when protonated ; also, zwitterions such as amino acids may change
from bound to unbound or vice versa, when they undergo charge inversion as a
function of pH .
Linear arrays of protonatable or hydrogen bonded sites may allow the directed
long range transfer of protons, thus functioning as proton-conducting channel, i.e .,
as proton wire . Relevant systems would be linear polyamines or polyphenolic con-
densed aromatic units [8 .218], self-assembled hydrogen bonded heterocyclic rib-
bons such as 116 (see Section 9 .4 .4) or polyelectrolyte membranes [8 .219] in which
collective proton motion may take place and lead to proton conductivity .
116
Multiple cyclic proton transfers occur in hydrogen bonded arrays of heterocyc-

lic units [8 .220, 8 .221] or inside rings such as porphyrins [8 .22] . Macrocyclic poly-
amines present various protonation patterns [3 .13a] that could be of interest as
information units . Data storage in a molecular "memory" by hole burning makes

use of proton transfer processes for instance, in porphyrins and hydrogen bonded
dye structures [8.96-8 .99, 8.223] . Proton transfer mediates charge transfer [8 .224]
and phase change [8 .225] in H-bonded solid molecular materials .
Photoinduced proton transfer may be generated through the large variation in
acidity or basicity of functional groups in the excited states of specific structures
[8.226] and lead to photoinduced pH jumps [8.227, 8 .228] . Changes of optical prop-
erties by tautomerisation in the excited state [8.229] occur, for instance, in the fluo-
rescent states of bipyridyl diols [8.230a] and form the basis of a proton transfer laser
process [8.230b] .
Of much significance is the realization of long-lived photogenerated tautomeric
states and long-range proton transfer (LRpT) processes . The latter could lead to
proton transfer charge separated states to be put in parallel with the extensively
studied charge separation by photoinduced electron transfer (see Section 8 .2 .3) . A
number of systems present photochromism on the basis of photoinduced proton
transfer [8 .229] .
In photosynthesis, light absorption results in charge separation by photoinduced
electron transfer . Realizing a proton-based analogue would be of much interest . The
first requirement is to devise systems presenting long-lived photoinduced tautomer-
ic states, compared with the very short lifetimes of the acid-base features of excited
states (for instance, in 2-naphthol) [8.226] . Significant progress towards such a goal
has been achieved by means of derivatives of the photochromotropic dinitrobenz-
yl-pyridine 117, which turns deep blue in the solid state on exposure to light and
reverts slowly to the colourless form in the dark [8 .231, 8 .232] . This colour change
results from a photoinduced proton transfer generating the tautomeric form 118 .
Irradiation of the phenanthroline analogue 119 has been found to give a tautomer
N02
NO2
N
H
0 NO2
® NO2
02N
119

8.5 Switching Devices and Signals . Semiochemistry
8.5.1 Switching Devices. Signals and Information
If the operation of the devices considered above on their specific substrate (photon,
electron, ion) is triggered by external optical, electrical or chemical stimuli, their fea-
tures may be switched between two (or more) states presenting different character-
istics. Such switching devices are therefore formed by two main components : a
trigger, the switching unit, activated by an external stimulus and a substrate, the
switched species ; they should operate with efficiency, reversibility and resistance to
fatigue .
The substrate carries information defined by its molecular recognition features
and constitutes a signal that may be modulated by the switching process . The stim-
ulus to which the switch responds and the substrate on which it operates may both
be either of photonic, electronic, ionic, magnetic, thermal or mechanical nature .
Thus, a whole set of switches based on (substrate-stimulus) pairs, is defined by the
combination of the various types : opto-photo, opto-electro, electro-photo, etc .
It is clear that the design of switched devices is intimately linked to the chemistry
of signal generation, processing, transfer, conversion and detection, i.e., to semio-
chemistry . The device is the effector generating a signal, the semiogen, and the sub-
strate is the carrier of the signal, the semiopbore (see Section 8 .1).
Switching also implies molecular and supramolecular bistability since it resides in
the reversible interconversion of a molecular species or supramolecular system be-
tween two thermally stable states by sweeping a given external stimulus or field .
Bistability in isolated molecules or supermolecules is, for instance, found in optical
systems such as photochromic [8 .229] or thermochromic substances or devices, in
electron transfer or magnetic processes [8 .239], in the internal transfer of a bound
substrate between the two binding sites of a ditopic receptor (see Section 4 .1 ; see
also Fig . 33) [6.77] . Bistability of polymolecular systems is of a supramolecular
nature as in a phase transition or a spin transition, both of which involve an assem-
bly of interacting species .
Multistability is present in systems that are interconvertible between more than
two states such as polynuclear--multivalence metal complexes or polytopic recep-
tors where one or more substrates may occupy and transfer between several differ-
ent binding sites.
Molecular hysteresis results when the interconversion between the states does not
follow the same pathway on sweeping the external stimulus or field in one or the
opposite directions [8 .240a, 8 .241] . A hysteresis loop has, for instance, been de-
scribed for the electrochemical interconversion of redox states in a dinuclear metal
complex; it involves the switching between two different binding sites [8 .240b] . Spin

8.5 Switching Devices and Signals . Semiochemistry 125
transition systems are of interest with respect to information storage and processing
[8 .24lb] ; a spin transition in a polymeric iron complex presents a thermal hysteresis
at room temperature [8 .241c] .
A hysteresis loop can formally be drawn for the interconversion of a photo-
chromic substance between two states A and B characterized by two well separated
absorption bands as shown in Figure 26 ; sweeping the frequency up from v„ to VA
converts the system from state A to B when v,, reaches the absorption band of A ;
the system remains in state B if v A goes back to v,,; sweeping v o to vB converts the
system from state B to A, where it remains when v goes back to tio . Such state inter-
conversion curves are also characterized by the non-linearity of the response with
respect to scanning the triggering stimulus .
Fig . 26. Formal photohystercsis

loop for the photochemical inter-
conversion of a photochromic sub-
A
stance between two states A and B
possessing two well separated active
absorption bands at frequencies vA
V
and vB (see text) . VB V0 VA
Signal conversion may be brought about when a device responds to a given stimu-
lus by generating a signal of another nature . Specific cases have already been men-
tioned above (Sections 8 .2 .3 and 8 .2 .4) . Substrate binding to a suitable receptor pos-
sessing a photoactive, a redox active, a proton exchanging site or a binding site for an-
other substrate may lead to modifications of the electrochemical, acid-base or bind-
ing properties, inducing the generation of a signal based on the release or the uptake
of a photon, an electron, a proton, an ion or a molecule, respectively (Figure 27) .
Logic devices may be designed on the basis of functional receptors that respond
differently to different substrates . A ditopic receptor responding differently when
either or both of two different substrates are bound represents an "AND" gate .
When the response is the same for two different substrates an "OR" function
results . When the binding is of sequential or cascade type (see Chapter 4), the bind-
ing of a second substrate requiring the prior binding of a first, an IF operation is
obtained, which also implies a regulation capability . The input-output may be opti-
cal, electronic or ionic . When the input is ionic (metal ions or molecular substrates)
and the output optical, photoionic logic devices are obtained . This is the case for
receptors responding to substrate binding by a change in light absorption or emis-

MOLECULAR
SIGNAL CONVERSION
SUPRA MOLECULAR
Modification Signal
Red - Ox
electron
9 Acid -Base proton

Elfeclor
Complexation ion
molecule
Fig. 27 . Schematic illustration of signal conversion processes ; binding of an effector to a

given site of a receptor in the resting state is accompanied by a change in redox, acid-base or
complexation activity at another site of the receptor and leads to the release of an electron, a
proton, an ion or a molecule .
TRANSFER AND READING OF INFORMATION
~ Fig. 28 . Schematic representation of

L'/ information and signal transfer by trans-
duction across a membrane by means of
molecular transmembrane rods ; (left) :
two possible in plane configurations with
cross sections of the rods ; (centre) : bind-
ing of the transmitter and receiver recep-
tors to the rods respectively on the left
and on the right of the membrane ; (right)
3D Structure + Kinetics (time) = 4 D Process other non-complementary receptors .
sion properties, like a change in fluorescence (see Section 8 .2 .2) as in the AND gate
based on the simultaneous binding of protons and sodium ions [8 .242] (see also
[8 .112e]) .
Transfer by transduction and reading of information and signals across a barrier
such as a membrane could beperformed following the principle illustrated in Figure2 8 .
A few transmembrane molecular rods having different lengths and terminal
shapes and moving freely by lateral diffusion may bind to a given receptor-trans-
mitter on one side (left) of the membrane in a configuration in the membrane plane
and in a displacement perpendicular to the membrane that will depend on the dis-
position and depth of the binding sites on the transmitter . This will impose on the

8. S Switching Devices and Signals. Semiochemistry 127
other side of the membrane a given topography for the set of rods that can be read
out selectively by binding of the complementary receptor-receiver . Such three
dimensional information transfer and reading should be highly efficient, selective
and economical . Indeed with only a few molecular rods an extremely large amount
of information may be expressed since the set of rods can adopt a very high num-
ber of topographies defined by in-plane configurations and out-of-plane displace-
ments . If, in addition, kinetic effects of association and dissociation rates come into
play, a 4D process results . The rods could be bolamphiphile molecules of different
shapes and nature .
The time modulation of transmitter signals, through pulsations of different dura-
tions and shapes may lead to frequency and amplitude coding of signalling events,
the detection requiring molecular receivers suitably tuned to frequency patterns and
thresholds . Such processes occur in intercellular communication by cell to cell sig-
nalling [8 .243].
Signal amplification is expected to take place when the triggering stimulus yields a
non-linear response as a function of the intensity (concentration) of the stimulus (sti-
mulating species) . This holds in systems displaying cooperativity and self -organiza-
tion, as in a phase change, for example . The chiral twisting of a mesomorphic phase to
become cholesteric on addition of a small amount of chiral component is such a case .
Stimulus induced perturbation of organized sup ramolec ular assemblies, such as opti-
cal switching of membrane self-assembly (see Section 8 .5 .5) or recognition-induced
formation of liquid crystalline polymers (see Section 9.4 .2), may be considered as an
amplification of a microscopic signal to the macroscopic scale . Positive cooperativity
is found in a polytopic ligand undergoing aggregation on ion binding [8 .2011 . Further
discussion of this and related questions will be given in Chapter 9.
8.5 .2 Photoswitching Devices
Most switching devices studied make use of light for interconverting a molecule be-
tween two different states . Both forward and backward processes may be photo-
induced or one of them, usually the reverse transformation, may be thermal .
Opto-photoswitching occurs in bistable photochromic substances [8 .229] that are
converted into a coloured form on irradiation and revert to the initial colourless or
less coloured state either thermally or on irradiation with light of another frequency .
Such substances and the materials they may form, for instance by combination with
polymeric matrices, are of great interest for optical data storage, in particular of
reversible nature [8 .244, 8 .245] . They should display (1) high quantum yields for
both forward and reverse processes; (2) well separated absorption bands in the two
states ; (3) high thermal stability ; (4) low fatigue on multiple cycling ; (5) read-out
capability without erasing; (6) rapid response ; (7) sensitivity to wavelengths of com-
monly used light sources such as red diode and green YAG lasers .

A number of photochromic systems have been extensively investigated that

undergo cis-trans isomerization (indigos, azo compounds) cleavage (spiropyrans),
electrocyclic processes (fulgides, 1,2-diarylethenes) [8 .229, 8 .244, 8 .245]. For
instance, cis-trans isomerization of a thio-indigo derivative allows the reading of
pyrene excimer or monomer fluorescence [8 .246]. The 1,2-dithienylethenc system
presents particularly attractive interconversion properties by photoreversible cyc-
litation [8 .245] .
F,lectro photoswitching devices possess a dual mode operation resulting from dif-
ferent electrochemical properties in the two photo-interconvertible states . They
may display both photochromism and electrochromism . They allow the photomo-
dulation of electrochemical properties as was shown to occur in photochromic
dihydroazulene derivatives [8 .247] . Separate photochemical and electrochemical
interconversion has been realized in systems containing a photoactive azo [8 .248,
8 .249] or dihydroazulene [8 .250] unit appended with an anthraquinone moiety .
Bis-pyridinium polyenes, the caroviologens [8 .140], may be considered as proto-
types of molecular wires, allowing electron flow to take place, [8 .143] and push-pull
polyenes present very pronounced non-linear optical properties [8 .88-8 .90] (see
Section 8 .2 .5) . The combination of these components with an externally triggered
switching process could lead to electro-photo or opto-photo switches . This may, in
principle, be achieved by inserting into the polvenic path a bistable "on/off" unit
that establishes or interrupts the electronic conjugation by reversible interconver-
sion between a closed and an open state, thus modulating electron conduction on
the one hand and NLO properties on the other (Figure 29) . Photomodulation of
electron conduction has been realized in a compound that undergoes reversible
interconversion between unconjugated 120a and conjugated 120b states by irradia-
tion in the UV and in the visible, respectively; 120b is easily reduced electrochemic-
ally, whereas 120a is not. Thus, the pair 120a /120b indeed represents a prototype of
a switched molecular wire [8 .25t] .
"OFF' "OFF'
All 01
..ON . 'ON'
Ga
Electron Conduction Non-Linear Optical Properties

(A and B are electroaclive groups) (0 and A are electron-donating
and withdrawing groups)
Fig. 29 . Optical switching of electronic conduction (left) and non-linear optical properties
(right) respectively in redox and push-pull polyenc molecular wires ; $ is the hyperpolariza-
bility.

8 .5 Switching Devices and Signals. Semiochemistry 129
FF FF
F F 365 rim F • F
> 600 n m l l
I~ S S S ;S 1
~N I ~N~ iN N~,
(open) (closed)
120a 120b
FF FF
F F 365 nm F F
F * F _ F • F
N > 600 nm ® S l , CN
S S S CN S S -' CN
S
(open) (closed)
121a 121h
Similarly, 121b possesses markedly enhanced optical non-linearity compared

with 121 a, thus displaying a photoswitching of NLO properties .
When the dithienylethene system bears two phenol groups, as in 122a, then
a dual-mode optical-electrical switching process is obtained combining photo-
chromism and electrochromismn . Compound 122a is photocyclized to 122b, which
can be electrochemically oxidized to the extended quinone 123; the latter is photo-
stable ; reduction of 123 back to 122b allows the photochemical opening to 122a
with visible light ; all three compounds have different absorption bands .
The special features of the three species are, in principle, well suited as basis of an
optical memory system with non-destructive write-read-erase capacity (see also
[8 .245]) . After photochemical writing with UV light (122a -) 122b), the informa-
tion may be "safeguarded" by an electrical process (122b -4 123) . It may then be
read many times and finally, after electroreductive unlocking (123 -> 122b), the
information may be erased with visible light (122b --> 122a) . This cyclic process
represents an EDRAW (Erase Direct Read After Write) process as compared to the
usual WORM (Write Once Read Many) process [8 .252].
It is clear that compounds based on the same principles as the present ones and
bearing various functional features (metal complexes, ionizable groups, energy and
electron transfer units) may be conceived, thus allowing for the reversible switching
of a variety of physicochemical properties . They provide entries, at the macroscopic
level, to materials for reversible information storage . At the microscopic level they
lead to molecular signalling processes and represent optically and electrically
addressable molecular switching devices .

130 8 Molecular and Supramnlecular Devices
FF FF
UV 312 nm
F * F (>96% conv .) F • F
® s s VIS >600 nm l S
o
S
l
HO OH HO OH
BIS-OH BIS-OH
(open) (closed) 122b
122a
electrochemically
inert E112 = - 180 mV
(-1 to +1 V range) (vs. SCE)
FF
I ~
VIS >600 nm F F
photochemically
inert
O S s •
le .- 100
BIS-Oq
123
Photochemical switching of the electrical properties of conductive Langmuir-

Blodgett films results from photoinduced conformational changes produced by an
azobenzene unit [8 .253] .
Electro-photoswitching devices represent means of generating photoinduced
electronic signals . Whereas controlled back and forth switching between two ther-
mally stable states is usually sought, fast switching is of interest for the design of
molecular electronic components operating on very short time scales . Long-lived
photoinduced charge separation is required for artificial photosynthetic investiga-
tions . Conversely, vectorial short-lived charge separation is desired for fast transfer
and switching of electronic signals . The numerous studies concerning photoindu-
ced electron transfer in metal complexes and in organic donor-acceptor systems are
of much value in this respect, even if it was often long-lived processes that were
sought (see Section 8 .2 .3) [8 .62-8 .68, A.10, A .20] . Picosecond optical switching in a
bis-porphyrin donor-acceptor-donor molecule has been described [8 .254] .
D-PS-A and D-bridge-A triads display similar properties (see Section 8 .2 .3)
[8 .255] . Systems presenting very long-range photoinduced charge separation allow
in principle the oriented transfer of electronic signals over long distances . For
instance, insertion into membranes represents a means of generating photoinduced
transmembrane signals . Such switching systems operate much faster than photo-
chromic species and contain no moving parts .

Photoswitching of ionic and mechanical processes, iono-photo and mechano-

photo switching, will be considered below.
8.5.3 Electroswitching Devices
Photo-electroswitching takes place in substances where an electrochemical change

induces more or less pronounced variations in light absorption or emission prop-
erties . This occurs namely for metal complexes subjected to redox interconversion
between their various oxidation states . A two-component device combining a lumi-
nescent centre and an electroactive unit may function as a photo-electroswitch in
which the emission properties are modulated by redox interconversion via energy
or electron transfer quenching (Figure 30) .
Electrochemical switching of the emission of a metal complex occurs in a system
in which a luminescent (tris-bipyridine)ruthenium(ii) centre is linked to a quinone
unit . Interconversion of the redox couple 124-125 allows the reversible switching
-e,+e
hV Redox energy or electron transfer

interconversion
EMISSION NO EMISSION
Fig. 30. Schematic representation of a photo-electroswitch where the emission properties

of a photosensitive centre are modulated by the electrochemical interconversion of a redox
centre inducing luminescence quenching by energy or electron transfer.
0 OH
O N I OH
a
(bpy2)Ru
2 PF6
2 PF6
124 125

between the luminescent hydroquinone 125 and the quinone 124 in which the lumi-
nescence is quenched by very fast electron transfer from the metal centre to the
organic acceptor unit .
The quinone-hydroquinone redox couple built into complexes 124 and 125 ful-
fils the requirements for the design of a bistable electro-photoswitch : both the oxi-
dized and reduced forms are isolable and stable ; the reduced form 125 is lumines-
cent, whereas the oxidized form 124 is quenched ; the electrochemical interconver-
sion of the two species is reversible [8 .256] .
Of much interest are the electroluminescence properties of conjugated polymers
that allow the development of electrically switched light-emitting devices [8 .257] .
Electric field activated bistable molecules are expected to switch at a critical field
strength [8 .258] .
Electroswitching of structure takes place when a redox change induces a revers-
ible structural or conformational process in a molecule, such as an electrochemically
activated intramolecular rearrangement [8 .259] . On the supramolecular level it con-
sists of the electroinduced interconversion between two states of different super-
structure . A case in point is the reversible interconversion of a double-helical
dinuclear Cu(t) complex M 2L 2 2 [8 .260] and of a mononuclear Cu(II) complex ML 2 +
in a sequential electrochemical-chemical process [8 .261] :
-2v
M 2 L, 2 + 2ML 2 + ( M = Cu ; L = quaterpyridine)
+2e
This process represents an elect roswitch 1 ng between a double helix and a single-
strand complex with interconversion of the ligand between a rather compact strand
state and a more extende double helical one (Figure 31) . It displays a sort of breath-
ing of the ligand and thus also constitutes a prototype for an electroswitched me-
chanical change (see Section 8 .5 .5) .
Electroswitching of molecular aggregate formation and disruption takes place on
interconversion of a lipid bearing a redox headgroup between a neutral and a
charged state, as for instance in hydrophobic ferrocene-ferricinium derivatives
[8.262, 8 .263] .
+ 2s
Fig . 31 . Electroswitching of a double helix-single strand interconversion between a double

helical dinuclear Cu(i) complex and a single strand Cu(11) complex in a sequential elc
e tro-
chemical-chemical process .

FF FF
UV 312 nm
F F (>98% cony .) F • F
® s
1% 1 `
s
VIS >600 nm 10,
$ s
Ho HO ON
BIS-OH °H BIS-OH
(open) (closed) 122b
122a
electrochemically
inert E112 =-180mV
(vs . SCE)
(-1 to +1 V range)
FF
F * F
~~ VIS >600 nm
photochemically ~- -
inert
0
BIS-Oq
123
Photochemical switching of the electrical properties of conductive Langmuir-

Blodgett films results from photoinduced conformational changes produced by an
azobenzene unit [8 .253] .
Electro-photoswitching devices represent means of generating photoinduced
electronic signals . Whereas controlled back and forth switching between two ther-
mally stable states is usually sought, fast switching is of interest for the design of
molecular electronic components operating on very short time scales . Long-lived
photoinduced charge separation is required for artificial photosynthetic investiga-
tions . Conversely, vectorial short-lived charge separation is desired for fast transfer
and switching of electronic signals . The numerous studies concerning photoindu-
ced electron transfer in metal complexes and in organic donor-acceptor systems are
of much value in this respect, even if it was often long-lived processes that were
sought (see Section 8 .2 .3) [8 .62-8 .68, A .10, A .20] . Picosecond optical switching in a
bis-porphyrin donor-acceptor-donor molecule has been described [8 .254] .
D-PS-A and D-bridge-A triads display similar properties (see Section 8 .2 .3)
[8 .255] . Systems presenting very long-range photoinduced charge separation allow
in principle the oriented transfer of electronic signals over long distances . For
instance, insertion into membranes represents a means of generating photoinduced
transmembrane signals . Such switching systems operate much faster than photo-
chromic species and contain no moving parts .

8 .5 Switching Devices and Signals. Semiochemistry 133
8.5.4 Switching of Ionic and Molecular Processes
Iono photoswitching, the photochemical switching of ion binding and transport

processes has already been considered in Sections 6 .4 .3 and 8 .2 .4 . The modulation
of ion binding strength by light provides a means for generating photoinduced ionic
signals in principle in a reversible and pulsed fashion .
The nature of the ion(s) and the frequency and amplitude coding of ionic pulses
may carry and process information, as in biological ionic processes [8 .243] . The af-
finity and selectivity changes in reported bistable photoactivated receptors for ions
and molecules are in most cases still quite small, but proper design should provide
a range of substances for the photogeneration of ionic and molecular signals .
The cis-trans photoisomerization of complexing agents containing a thioindigo
unit leads to changes in ion binding and transport properties [8 .264-8 .266]. Other
systems could be based on the photoelectrocyclic isomerization of 1,2-diarylethyl-
enes such as in 120a-120b .
Complexes of photocleavable chelating ligands release irreversibly-bound diva-
lent cations (calcium, magnesium) on irradiation [8 .267, 8 .268] . Photocleavable
macrobicyclic cryptands [8 .269] generate selective photoionicsignals. On irradiation
of the cryptate 126 cleavage of one of the bridges of the macrobicycle occurs thus
releasing the bound cation . The process is very efficient due to the high binding con-
stants of the cryptatcs and the large change in affinity that occurs on cleavage (from
104-10 5 M -1 to less than about 10 M-t ), thus leading to a large concentration jump
(Figure 32).
n+
126
In principle, any cation cryptate (see Section 2.3) can be treated in this way, thus
allowing the initation of ion transport and cellular ion regulation processes by a light
pulse [8.48b, 8 .270, 8 .271] . The same type of approach can be applied to anions and
molecular substrates by incorporating the photocleaving unit into the correspond-
ing receptor molecule (macrobicyclic polyamine for anions [8 .272], cyclophane
receptor for hydrophobic molecules, for instance) . Photosensitive protecting
groups allow the photogencration of a free species like ATP, nucleotides, etc.

n+
02N
KS
ON
300-360nm
0=
0 OH
r7 +
N
<~0 / >
0-,
Fig. 32 . Generation of photoionic signals by photodeavagc of a macrobicyclic cation cryp-

tate; the cation can be any one of those forming a cryptate.
[8 .273] . Such photorelease of various substrates is of much interest for the study of
both semiochemical processes and biological regulation and communication .
Photoprotonic signals can be generated by light induced proton release, this might
happen for the quaternary N-R+ derivatives of 117, for instance [8 .233] . The pho-
toproduction of proton gradients across membranes could serve as a light-powered
proton pump for inducing vectorial processes such as the transport of protons
[8 .233, 8.234] or H+-ATPase model reactions [8 .274] .
Ion switches may be based on ionic jumps inside polytopic ligands between
different sites presenting different optical or electrochemical properties . Iono-
electroswitching, for instance, is produced by redox interconversion of a given
cation between two different sites providing suitable binding for two different oxi-
dation states in a ditopic receptor . This could occur in heteroditopic receptors, such
as that in 47 or a macrotricycle of type 46 with two different rings (N 2S2 and N20 3,
for example) (see Figure 33) . Such a complex should possess different optical prop-
erties in each site so that electroswitching would interconvert two species in which
the different locations of the ion would correspond to different optical signals .
Redox triggered iron translocation takes place in triple-stranded helical complexes
[8 .275] .

8.5 Switching Devices and Signals . Semwchcmistry 135
I+ 2+
N
NF S
-e
.e
~N NJ
~. uJ
Fig. 33. A potential iono- or mechano-electroswitch based on a heterotopic macrotricyclic
ligand ; the electrochemical interconversion of a copper ion could switch the location of the
ion from the [12]-N2S2 ring in the Cu(i) state (left) to the [151-N203 subunit in the Cu(i1)
state (right).
Electroaonic signals are generated by electrochemical interconversion of a selec-

tive receptor molecule containing a redox-active group (metallocene, quinone, etc .)
between states of low and high affinity for a given substrate (see Sections 6 .4 .1 and
8 .3 .1) .
iono-ionoswitching, i .e . ionic switching of ionic processes, takes place when the
binding of a given species interferes with that of another. Ditopic ligands may pres-
ent allosteric effects leading to ionic modulation of affinities and thus to ion uptake
or release when the binding of a first species affects that of the next [8 .211, 8 .276] .
Proton transfer causes proton-induced switching of metal-metal interaction in
dinuclear complexes [8 .277a] and substrate binding to the curcurbituril receptor is
modulated by pH in a bimodal fashion [8 .277b] .
8 .5.5 Mechanical Switching Processes
Positional changes of atoms in a molecule or supermolecule correspond on the molec-

ular scale to mechanical processes at the macroscopic level . One may therefore im-
agine the engineering of molecular "machines" that would be thermally, photochem-
ically or electrochemically activated [1 .7,1 .9, 8 .3, 8 .109, 8 .278] . Mechanical switching
processes consist of the reversible conversion of a bistable (or multistable) entity be-
tween two (or more) structurally or conformationally different states . Hindered
internal rotation, configurational changes (for instance, cis-trans isomerization in
azobenzene derivatives), intercomponent reorientations in supramolecular species
(see Section 4 .5) embody mechanical aspects of molecular behaviour.
Although they are random and not oriented, the motions of a substrate inside a
cyclodextrin cavity (see Section 4 .5) have molecular ball-bearing flavour . Correlat-

ed internal rotations between bulky groups presenting conformational gearing has

the character of cogwheel processes at the molecular level [8 .279a] and a molecular
brake activated by metal ion binding has been described [8 .279b] . Mechanical move-
ment is produced in a protein by the proline switch that is operated by the pepti-
dyl-prolyl cis-trans isomerases [8 .279c] . Mechanical bistability is represented by the
orientational isomers of guests in carceplexes [8 .279d] . Mechanical analogies are also
displayed by threade and interlocked systems such as rotaxanes and catenanes
[8 .280-8 .284] (see also Section 9.6 .2), which are by construction mechanical objects
of supramolecular nature . This is the case for the thermally activated motions of one
ring around the other in a [2]-catenane [8 .285a] and the shift of a ring along posi-
tions around a large ring in a "molecular train" fashion [8 .285b] . Similar shifting of
a ring between binding positions in a rotaxane represents a molecular shuttle or a
sort of (supra) "molecular abacus" [8 .286, 8 .287] . Formally such motions are also
related to ion jumping between sites in polytopic receptors (see above) . These pro-
cesses are all thermally activated . A further step will be to go from random back-
and-forth displacements to oriented motions .
Mechano photoswitching takes place in photoswitchable [2]-catenanes incorpo-
rating an azobenzene unit [8 .2881 and in a photoactivated molecular shuttle [8 .289a] .
The latter might he developed into a light-driven version of a supramolecular aba-
cus as schematically represented in 127 . Such developments point to thermally or
photochemically activated mechanical switching devices for information storage and I
processing .
127
Mechano-electroswitching has been mentioned above (see section 8 .5 .3) (Figure

31) . It takes place in the electrochemically (or chemically) triggered positional
switching of the macrocycle along the threade chain in a rotaxane [8 .289b] . It may
also be considered to occur when bound cations can be brought to shift from one
site to another in a polytopic receptor by redox triggering due to the dependence of
coordination geometry and binding preference on the oxidation state (see
iono-electroswitching above) .
Mechano-ionoswitching takes place, for instance, in polytopic ligands presenting
ion binding induced allosteric changes [8 .201, 8.276] or when an ion binds to a
catenand to form a catenate [8 .281, 8 .282] . Modulation of the binding of a second
substrate may be brought about .

Large structural changes occur on binding of metal cations to polyethylene

oxide) [8 .197], in the cooperative transition from a globular neutral form to an
extended coil displayed by hydrophobic polyamines on protonation [8 .290] or in
stimuli-responsive self-organized systems such as liquid crystals, micelles, vesicles
monolayers [8 .291] and gels [8 .292] (see also [8 .262, 8 .263]) . Triggering supramolec-
ular assemblies by optical, electrical or chemical stimuli may result in a large scale
change of the organization, thus amounting to signal amplification to and expres-
sion on the macroscopic level . Such effects are of interest for the development of
chemo-mechanical actuators for the conversion of light, electrical or chemical
energy into mechanical energy and motion, a major goal being, as already pointed
out, to achieve controlled oriented motion . Biological chemo--mechanical energy
transduction occurs in the actomyosin molecular motor on muscle action [8 .293]
and more generally in the production of motion in living organisms from reversible
chemical changes [8.294] .
In general, optically, electrically or chemically triggered switches would seem to
be preferable to mechanically activated ones, as are photo-, electro- and chemo
devices with respect to mechano devices and electronic or photonic computing with
respect to mechanical computing . The ultimate in (nano)mechanical manipulation
of a molecular device is represented by the realization of a bistable switch based on
the motion of a single atom by means of the scanning tunnelling microscope [8 .295]
(see also Section 9.9).
There is clearly a vast domain of investigation into the design and properties of
molecular and supramolecular devices as basis for the development of chemical
information processing and signalling as well as for the exploration of their rela-
tionships with related biological phenomena . One may envisage connecting arti-
ficial devices and biological entities, such as field effect transistors and neural cells
[8 .296], as well as the use of biological molecules for the engineering of devices, as
in chip construction by DNA technology [8 .297] .
A highly relevant question is whether the goal should be to operate at the level of
the single component or not . In order to minimize the risk of device failure the incor-
poration of some redundancy or repair procedures appears unavoidable, as in biolog-
ical processes, so that it will be necessary to develop suitable addressing and detection
procedures, error-checking and self-healing mechanisms for multidevice arrays .
Methods for analysing the response of complex multicomponent-multifunction-
al systems will be needed . Global responses may be submitted to deconvolution
procedures and multicomponent analysis [8 .298], making use for instance of pattern
recognition [8 .238, 8 .299], neural network [8 .238, 8 .300] and fuzzy logic [8 .301]
approaches .
The formation of photonic, electronic, ionic switching devices from molecular
components and their incorporation into well-defined organized assemblies repre-
sents the next step towards the development of circuitry and functional materials at

the nanometric scale . This involves suprarnolecular engineering in the polymolec-

ular state, at interfaces or in the bulk, for instance in functionalized Langmuir- I
Blodgett films (see Chapter 7, Section 9.7) . The controlled build-up of such archi-
tectures requires the ability to direct self-assembly and self-organization processes
through explicit instructed procedures .

Quimica Spramolecular Chapter 8 M.J. Lehn Supramolecular Chemistry

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8.

mized for a given purpose (wavelength of absorbed or emitted light ; lifetime of

h v' Eu3 + included

analogous luminescent proerties [8 .18]. Di- and trinuclear complexes, such as

between a group 87 and an acceptor A (such as allophycocyanine) borne each by a

Polymetallic complexes presenting directional energy migration are of much sig-

8.2 .2 Photosensitive Molecular Receptors

Receptor molecules bearing photosensitive groups may display marked modifica-

96 8 Molecular and Supramolecular Devices

ᖻ.2 Supramolecular Photochemistry ᖻᖻ

The macrotricyclic receptor ᖻ2 displays fluorescence detection of linear recognition

ᖻ.2.ᖻ Photoinduced Electron Transfer in Photoactive Devices

Light absorption, by markedly affecting the electronic properties of molecules and

98 8 Molecular and Supramolecular Devices

ELECTRON TRANSFER RECOMBI NATION

Fig. 19 . Schematic representation of a center for photoinduced charge separation consisting

complexes [8 .69c] . In this respect, organized supramolecular assemblies have been

8.2 Suprarnolecular Photocbemistry 99

8 .2.4 Photoinduced Reactions in Supramolecular Species

Receptor molecules containing suitable light-sensitive groups may undergo photo-

100 8 Molecular and Supramolecular Devices

8.2 .5 Non-Linear Optical Properties of Supramolecular Species

Organic and inorganic substances presenting a large electronic polarizability are

8.2 Suprarnolecular Photochemistry 101

cients, is sought . At the supramolecular level, it is necessary to achieve a high

Fig . 20 . Two series of donor-acceptor polyconjugated molecules bearing a ben7 .odirhia or

102 8 Molecular and Supramolecular Devices

If a highly polarizable group is introduced into a receptor molecule, substrate

8.2 Supramolecular Photochemistry 103

8.2 .6 Supramolecular Effects in Photochemical Hole Burning

Dye molecules incorporated in a crystalline or amorphous (polymer or glass) solid

The photochemical and photophysical processes discussed above provide illu-

mation into photosignals .Thusmolecardign,stvermolcuabndig,

8.3 Molecular and Supramolecular Electronic Devices 105

8.3 .1 Supramolecular Electrochemistry

106 8 Molecular and Supramolecular Devices

Systems presenting many identical redox-active components bound to a central

8 .3 .2 Electron Conducting Devices . Molecular Wires

Among the various devices and components performing molecular-scale electronic

8.3 molecular and Supramolecular Electronic Devices 107

Electron-transfer experiments employing the CV2+/dihexadecyl phosphate

108 8 Molecular and Supramolecular Devices

Fig. 22 . Schematic representation of transmembrane electron transfer from a reducing

But But Bu' Bu' Bu' Bu' Bu' But

B"I * / \ 0 Bow * 11 0 Bu'Bu' l 10 Bu'But * l, 4 Bu'

8.3 Molecular and Supramolecular Electronic Devices 109

bicyclo[1 .1 .1]propellane ("staffanes") [8 .153], bicyclo[2 .2 .2]octane [8 .154] and car-

110 8 Molecular and Supramolecular Devices

n-B n-B n-Bu -Bu

8.3 Molecular and Supramolecular Electronic Devices 111

8.3 .3 Polarized Molecular Wires . Rectifying Devices

Conjugated polyolefinic chains bearing an electron-acceptor group on one end and

8.3 .4 Modified and Switchable Molecular Wires

112 8 Molecular and Supramolecular Devices

may act as photoactivated molecular wires in bilayers [8 .168] capable of generating

8.4 Molecular and Supramolecular Ionic Devices 113

8.3 .5 Molecular Magnetic Devices

Molecular magnetism [8 .174] is by essence of supramolecular nature since it results

8.4 Molecular and Supramolecular Ionic Devices

8.4 Molecular and Supramolecular Ionic Devices 115

TYPES of ION CHANNEL STRUCTURES

STACK STRING RACK PIPE SPRING SPLIT BUNDLE BOUQUET

116 8 Molecular and Supramolecular Devices